Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0096—Purification; Precipitation; Filtration
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B69/00—Dyes not provided for by a single group of this subclass
  • C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
  • C09B69/04—Dyestuff salts, e.g. salts of acid dyes with basic dyes of anionic dyes with nitrogen containing compounds

Definitions

• This invention relates to solid complexes of anionic organic dyes with quaternary ammonium compounds which are have average molecular weights of below about 900 which are substantially free from unwanted salts.
• quaternary ammonium compounds are those which comprise alkoxylated moieties.
• Such complexes are formed through ionic bonds formed between the two compounds.
• the complexes are then removed of substantially all resultant unwanted salt formed from the cations of the dye and the counter-ions of the quat so as to obtain a solid dyeing agent which easily disperses within different media and which possess extremely good non-migration and coloring characteristics.
• This invention also concerns methods of making the aforementioned salt-free solid anionic dye/quat complexes as well as methods of utilizing such complexes for dyeing thermoplastic, thermoset, and wax compositions.
• Quaternary ammonium compounds are well known as complexing agents for anionic dyes.
• U.S. Pat. No. 5,059,244, to King discloses an aqueous solution of anionic dyes and an ethoxylated triethanolamine. This composition is useful as an ingredient within ink formulations and as an agent for temporarily tinting textile fibers; however patentee neither teaches nor fairly suggests removing any excess inorganic salts.
• Quaternary ammonium compounds have been disclosed as useful auxiliary agents for printing on fiber materials.
• U.S. Pat. No. 3,785,767, to Hildebrand discloses a pad-steaming process for the continuous dyeing and printing of fiber material with a formulation containing anionic dyes and amine salts.
• Anionic dyes in particular acid dyes (i.e., those containing sulfonic or carboxylic acid moieties) provide desirable and beneficial coloring characteristics to many different types of substrates.
• acid dyes i.e., those containing sulfonic or carboxylic acid moieties
• beneficial dyes with acceptable coloring performance, within certain media, such as waxes, polyolefins, polyurethanes, hydrocarbons, and the like.
• the polarity (hydrophilicity) of such acid dyes is sufficiently high so as to prevent long-lasting dyeing or even any coloring at all within such media.
• the simplest manner of practicing the invention is first determine the desired anionic dye for its shade, lightfastness, thermal stability, and the like, for the subject substrate to be colored; second, select the appropriate quaternary ammonium compound, with a molecular weight of below about 900, for the subject substrate based on the necessarily required physical properties such as migration, uniform dispersion, solubility, washfastness, and the like; third, react the two compounds together to form a solid colorant; and last, remove the unwanted salts formed from the cation of the dye and the counter-ion of the quat.
• a further objective of this invention is to provide a polymeric colorant which can be used in dyeing hydrocarbons, thermoplastics, thermosets, and waxes, as well as within ink-jet and printing ink formulations and applications.
• inventive colorant complexes are those which produce color in the visible spectrum and comprise quaternary ammonium compounds having average molecular weights of at most 900; preferably at most 500; more preferably at most 450; and most preferably at most 300.
• Specifically preferred quats include dicoco dimethyl ammonium chloride (sold under the trade name Adogen® 462).
• the inventive colorant complexes are those which produce colors within the visible spectrum and thus specifically do not include whitening agents, optical brighteners, ultra violet absorbers, and the like.
• the previously taught anionic dyes/quaternary ammonium compound complexes are typically not purified and may contain relatively large amounts (generally from about 1 to about 50%) of unwanted cation/counter-ion salts.
• Such salts may be strictly inorganic in nature or may comprise organic cations or organic counter-ions as well.
• Some salts are typically present within acid dye compositions as byproducts from manufacturing processes as well as diluents which provide the capability to level the color strength.
• Typical inorganic salts are sodium sulfate and sodium chloride, however many other different salts, including organic salts, as noted above, may also be present. As discussed in greater detail below, such unwanted salts are also byproducts from the complexation between anionic dyes and quaternary ammonium compounds. With the presence of such unwanted salts in the composition, either the quaternary ammonium compounds or the inorganic cations may serve as counter ions for the complexed anionic dyes. As a result, the chances for continued complexation between the dye and quat components decreases with the presence of increased amounts of inorganic salts.
• salt-containing acid dye/quat complex colorant systems show uneven solubility and poor dispersability in different organic media, such as plastics, waxes, coating systems, and organic solvents.
• Such complexes are therefore neither suitable as dyes or colorants for thermoplastics, thermosets, or waxes, nor as colorants within ink-jet and printing applications and formulations. Therefore, the term "substantially salt-free" as used in the context of this invention is intended to mean a complex which is substantially free from these unwanted cation/counter-ion salts.
• a substantially salt-free solid anionic organic dye/quaternary ammonium complex colorant wherein the quaternary ammonium compound has a relatively low molecular weight, provides favorable non-migration and coloring characteristics within thermoplastics, thermosets, and waxes, as well as within ink-jet and printing applications and formulations.
• the removal of unwanted salts provides an improved stability for the complexes.
• Such a complex has excellent dispersability and solubility in plastics, water, organic solvents, and coating systems.
• the physical properties of the complex can be tailored to any particular requirement by altering the structure of the quaternary ammonium compound.
• a more hydrophobic quaternary ammonium structure affords the user, upon complexation with an anionic dye and removal of substantially all of the resultant salt, a colorant which is more soluble within organic solvents, waxes, and plastics, such as polyolefins, polyurethanes, and polyesters.
• inventive solid inorganic salt-free complexes can be dissolved in various solvents, diluents, and carrier systems. Such liquid solutions facilitate handling, processing, and manufacturing in a large-scale industrial setting.
• Plastics both thermoplastics and thermosets, are typically dyed by adding a pigment or dyestuff to the resins.
• the incorporation of pigments into plastics might adversely impact the physical properties of plastics. If a conventional dyestuff is employed, water resistance, oil resistance and the migration of the dyestuff may often be disadvantageously inadequate.
• One definite improvement in coloration of plastics is set forth in U.S. Pat. Nos. 4,640,690, to Baumgartner et al., and 4,507,407, to Kluger et al., in which liquid polymeric colorants are added to the resin before or during compounding and polymeric addition reaction.
• polymeric colorants disclosed in these references may be broadly described as polyalkyleneoxy-substituted chromophore groups. Colorants of this general class are well known and have been disclosed as fugitive tints in U.S. Pat. No. 3,156,663 to Kuhn, as merely one example. Even though the polymeric colorant represents a vast improvement over prior arts, the actual number of chromophores which can be adapted to this technique is limited due to the lack of available polymeric intermediates.
• inventive complexes can be used for dyeing many different and diverse media, including thermoplastic composites, thermosets, and waxes, and can also be utilized within printing ink formulations, all as merely examples.
• inventive complexes possess the advantageous properties of polymeric colorants such as high tint strength, desirable migratory properties, and minimal impact on the physical properties of plastics.
• chromophores can be adopted to practice this invention.
• anionic dyes such as acid dyes, direct dyes and certain food dyes, are useful within the inventive salt-free complexes.
• Such chromophore molecules preferably have at least one reactive site (such as a sulfonic or carboxylic acid functionality) in order to form the necessary complex with the quaternary ammonium compound.
• the cationic ammonium group bonds with such acid (i.e., sulfonic and/or carboxylic) groups through ionic bonds. It is not fully understood how the interaction between the cationic moiety of the quaternary ammonium and the anionic moieties of the anionic dyes is accomplished; however, as discussed above, it is evident that the quaternary ammonium compound has a greater affinity for the anionic dye rather than for the anionic counter ion to which such quats are generally bonded.
• the anionic dye which has more of an affinity for the cationic quat rather than for the cationic counter ion.
• the free counter ions of both components react together to form the aforementioned unwanted salts which require removal (at least to a substantial extent) from the resultant complex in order to provide the desired aforementioned beneficial properties.
• the permissible level of remaining salt, and thus the definition of substantially salt-free for this invention, within the inventive complex is, at most, about 5,000 ppm. In theory, it is impossible to remove all of the unwanted salt from such complexes; however, at such low, permissible, and attainable levels of salt content, the desired migration and colorant characteristics may be obtained. Certainly, a level of no salt at all would be most preferred, although such a level is, as noted above, nearly impossible to achieve.
• a wide range of quaternary ammonium compounds have been shown to be useful for practicing the invention.
• a broad list of potentially useful quats within this invention include trialkyl, dialkyl, dialkoxy alkyl, monoalkoxy, mono-substituted polyalkoxy alkyl, di-substituted polyalkoxy alkyl, tri-substituted polyalkoxy alkyl, benzyl, and imidazolinium quatenary ammonium compounds.
• the particularly preferred quats are noted below as this is merely a broad list of different classes of quaternary ammonium compounds which may be useful within the inventive complex and method.
• Chromophores containing at least one sulfonic acid or carboxylic acid functionality are preferred and are most suitable within this invention.
• the acid functionality may be directly coupled to the chromophore or to a substituent on the chromophore.
• suitable chromophores are acid dyes and direct dyes.
• quaternary ammonium compounds can be adapted to the invention herein with success.
• the quaternary ammonium compounds are analogs of ammonium salts in which organic radicals have been substituted for all four hydrogens of the original ammonium cation.
• Substituents may be alkyl, aryl, aralkyl, or alkoxylate groups, or the nitrogen may be part of a ring system.
• TABLE 2 a list of preferred classes and examples of quaternary ammonium compounds is set forth in TABLE 2 below:
• any such compound which has an average molecular weight of below about 900 and produces a solid compound upon complexation with an anionic dye is encompassed within the scope of this invention.
• the amount of residual inorganic salts is generally between about 50 ppb and 5000 ppm.
• sodium counter-ions, and thus sodium salts are the residual inorganic ions and salts within such anionic dyes.
• Monitoring of the inorganic salt level is available through conveniently and easily performed measurements of the sodium ion level within the composition.
• Various purification techniques may be performed in order to remove substantially all of the residual inorganic salts from the complexes.
• Such techniques include, but are not limited to, solvent extraction, phase separation, and filtration methods.
• Ultrafiltration does not work very well to remove the unwanted salts since the colorants are solids and most of the inventive colorant complexes are not very soluble in water.
• Particularly preferred are phase separation through the utilization of an ammonium carbonate rinsing procedure (i.e., three consecutive washings with 25% aqueous ammonium carbonate in a 1:1 weight ratio to complex), and solvent extraction filtration through the utilization of methylene chloride.
• the resultant purified solid colorant complex is water-insoluble
• a simple wash with water can be performed in order to remove the water-soluble excess inorganic salts.
• the resultant solution should also be stripped of excess water in order to purify the colorant complex.
• the inventive complexes will always form a solid upon purification, particularly at ambient temperature and pressure.
• Direct blue 86 11.8 g of Direct blue 86 were dissolved in 100 ml water. To the solution was added 15.04 g of Adogen® 470 (ditallow dimethyl ammonium chloride). This composition was then stirred at 50° C. for 1 hour. The mixture was then subjected to methylene chloride extraction twice. The two methylene chloride solutions were then combined and stripped under vacuum to produce a dark cyan wax colorant. 30 mL of sorbitan monooleate surfactant (available from ICI under the trade name SpanTM 80) was then added to the wax colorant and this solution was stirred at 80° C. for one hour to subsequently produce a cyan liquid.
• Adogen® 470 distethoxymethyl ammonium chloride
• Acid Red 1 10.0 g of Acid Red 1 were dissolved in 150 mL of water with stirring and heated to 50° C. To this stirred composition was added a mixture of 20.3 g of Adogen® 462 (75% active) and the mixture was subsequently heated to 70° C. and stirred for another 30 minutes. Upon standing, the mixture separated into two distinct layers. The aqueous layer containing the dissolved excess unwanted cation/counter-ion salt was discarded and the remaining product layer was evaporated to dryness to produce a dark red, stiff, waxy, non-flowable colorant.
• the addition of the sorbitan monooleate within the initial complex facilitated the phase separation for purification.
• Such an addition of surfactant may be performed either in this initial reaction stage or after the complex has been formed.
• the subsequent addition permits the formation of an easily handled and processed liquid dispersion of the inventive solid colorant complex.
• EXAMPLE 3 The colorant of EXAMPLE 3 was added to 40 grams of molten votive candle wax and stirred at 90° for 30 minutes. The wax mixture was then poured into molds and allowed to solidify. This produced a dark red candle having uniform color throughout the entire product and having no tendency to migrate into the plastic overwrap in which such candles are commonly packaged.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Coloring (AREA)
• Pyridine Compounds (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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Citations (17)

• 1998
  • 1998-04-24 US US09/065,620 patent/US5938828A/en not_active Expired - Lifetime
• 1999
  • 1999-04-14 BR BR9910143-2A patent/BR9910143A/pt not_active IP Right Cessation
  • 1999-04-14 CA CA002329917A patent/CA2329917A1/en not_active Abandoned
  • 1999-04-14 JP JP2000545940A patent/JP2002513065A/ja active Pending
  • 1999-04-14 AU AU36436/99A patent/AU3643699A/en not_active Abandoned
  • 1999-04-14 CN CN99806817A patent/CN1303418A/zh active Pending
  • 1999-04-14 WO PCT/US1999/008187 patent/WO1999055787A1/en not_active Application Discontinuation
  • 1999-04-14 EP EP99918555A patent/EP1088039A1/en not_active Withdrawn

Patent Citations (17)

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